CN100368573C - Copper-base lump non-crystalline alloy - Google Patents
Copper-base lump non-crystalline alloy Download PDFInfo
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- CN100368573C CN100368573C CNB2005100462567A CN200510046256A CN100368573C CN 100368573 C CN100368573 C CN 100368573C CN B2005100462567 A CNB2005100462567 A CN B2005100462567A CN 200510046256 A CN200510046256 A CN 200510046256A CN 100368573 C CN100368573 C CN 100368573C
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- alloy
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- crystalline alloy
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- base lump
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000010891 electric arc Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 15
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229910017532 Cu-Be Inorganic materials 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000004781 supercooling Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 238000007496 glass forming Methods 0.000 description 4
- 208000010392 Bone Fractures Diseases 0.000 description 3
- 206010017076 Fracture Diseases 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 206010010214 Compression fracture Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910018100 Ni-Sn Inorganic materials 0.000 description 1
- 229910018532 Ni—Sn Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
The present invention relates to Cu-base block-shaped non-crystalline alloy. The main components of the block-shaped non-crystal are Cu, Zr, Al and Gd. The forming dimension of the non-crystalline alloy is increased to 8mm from 3mm by the Gd element replacing the Zr element in Cu45Zr47Al7 alloy. The preparing method of the Cu-base block-shaped non-crystalline alloy is copper mould casting method. The novel Cu-base block-shaped non-crystal of the present invention has good performance for forming glass. In addition, compared with traditional Cu-Be alloy, the Cu-base block-shaped non-crystalline alloy has higher strength for preventing compression and break and has certain practical value.
Description
Technical field:
The present invention relates to the Cu base lump non-crystalline alloy, a kind of novel Cu base lump non-crystalline alloy is provided especially.
Background technology:
Because blocky metal-glass has excellent mechanical property (high strength, high rigidity, high corrosion resistance etc.), magnetic performance and corrosive nature, so blocky metal-glass just becomes one of focus of world's material circle research through finding.With respect to the Zr base, blocky metal-glass such as Mg base, the discovery of Cu matrix shape metallic glass is than later.Nineteen ninety-five, California Inst Tech USA takes the lead in preparing Cu matrix shape metallic glass, that is: Cu
47Zr
12Ti
33Ni
8Blocky metal-glass.Afterwards, the investigator found that Cu-Ti-Zr-Si-B alloy and Cu-Ti-Zr-Ni-Sn alloy also had higher blocky metal-glass and form ability, but the content of metal Cu is 40at% approximately only in these alloy systems.The blocky metal-glass of high Cu content is at first to be reported by Inoue group of northeastern Japan university in calendar year 2001: composition is Cu
60Zr
30Ti
10Alloy have very high glass forming ability, its maximum critical cast diameter reaches 4mm.On this alloy basis, the investigator finds that the adding of oligo-elements Y, element Be, element S n has increased Cu
60Zr
30Ti
10The glass forming ability of alloy, maximum non-crystalline state sample diameter reaches 5mm.Similar with the Cu-Zr-Ti alloy system, the Cu-Hf-Ti alloy system also has higher glass forming ability.In addition, the investigator finds that Cu-Zr-Al alloy system, Cu-Hf-Al alloy system utilize the method for copper mold casting can obtain the blocky metal-glass of 2～3mm.
Summary of the invention:
The objective of the invention is to obtain a kind of Cu base lump non-crystalline alloy, the more original alloy of its glass forming ability improves a lot; Compare with traditional copper alloy, mechanical property is improved; Compare with other alloy system, cheap.
The invention provides a kind of Cu base lump non-crystalline alloy, it is characterized in that: this bulk amorphous alloy is mainly elementary composition by Cu, Zr, four kinds of Al, Gd, the concrete content of each element is Zr, the Al of 3～10% atoms, the Gd of 0.2～10% atom of 40～50% atoms, the Cu of surplus.The elementary composition scope of preferable each is: the Al of the Zr of 44.5～45.5% atoms, 6.5～7.5% atoms, the Gd of 1.5～2.5% atoms, the Cu of surplus.
The present invention also provides the preparation method of above-mentioned Cu base lump non-crystalline alloy, it is characterized in that:
---surperficial non-oxidation, no greasy purity are carried out the weighing mixing greater than four kinds of elements of Cu, Zr, Al, Gd of 99.9%, in the copper crucible in the electric arc furnace that has oxygen absorbent of packing into, in high-purity inert atmosphere, carry out melt back, obtain mother alloy;
---described mother alloy packed into to be had in the silica tube of nozzle, puts into induction furnace and carries out induction melting, in high-purity inert atmosphere, with pressure fused mother alloy molten metal is sprayed in the round-meshed red copper mould, and Circularhole diameter is 2～10mm.
Among the preparation method of Cu base lump non-crystalline alloy of the present invention, described oxygen absorbent is preferably spongy surface Ti, and high-purity indifferent gas is an argon gas.
Among the preparation method of Cu base lump non-crystalline alloy of the present invention, preferably melt back is 4 times, and pressure is 1 ± 0.3MPa.
Among the preparation method of Cu base lump non-crystalline alloy of the present invention, the stock chart surface oxidized skin should be removed; Putting into sherwood oil again carries out ultrasonic cleaning and removes its surperficial grease.
The present invention adopts the copper mold teeming practice to prepare large-sized Cu base lump non-crystalline alloy, makes original Cu
45Zr
47Al
L7Alloy amorphous formation ability improves greatly.Can confirm that through X diffraction and isothermal differential thermal analysis the diameter of acquisition is that the diffraction curve of 8mm amorphous bar has typical amorphous characteristic.The glass transition point and the thermostability parameter of this amorphous bulk have further been obtained by differential thermal analysis.Thermoanalytical temperature range is: 150～1200 ℃; Temperature rise rate is 20K/min.The DSC curve that obtains the significantly heat absorption phenomenon relevant with glass transition appears.To the acquisition diameter is that the non-crystal bar of 2.5mm carries out the measurement of mechanical property, and experiment condition is: room temperature; Compression speed: 1 * 10
-4S
-1By SEM the compression fracture is analyzed in addition.Performance index are:
Form size :～8mm
Glass transformation temperature (T
g): 650700K
Initial crystallization temperature (T
x): 720～800K
Temperature of fusion (the T of bulk amorphous alloy
m): 960～1120K
Liquidus temperature (the T of bulk amorphous alloy
1): 1150～1200K
Yield strength: 1600～1700MPa
Fracture compressive strength: 1800～2100MPa
The present invention has the following advantages:
1. compare with the Zr base noncrystal alloy, cheap.
2. the amorphous formation ability height has the supercooling liquid phase region of broad, Heat stability is good.
3. with traditional Cu-Be alloy phase comparison, has higher compressed rupture strength.
Description of drawings:
Fig. 1 is different diameter Cu
46Zr
45Al
7Gd
2The XRD curve of bulk amorphous alloy;
Fig. 2 is Cu
46Zr
45Al
7Gd
2The low temperature of bulk amorphous alloy and at the isothermal DSC curve of 738K;
Fig. 3 is Cu
46Zr
45Al
7Gd
2The high temperature DSC curve of bulk amorphous alloy;
Fig. 4 is Cu
46Zr
45Al
7Gd
2The compression curve of bulk amorphous alloy;
Fig. 5 is Cu
46Zr
45Al
7Gd
2The macrofracture pattern of bulk amorphous alloy compression sample;
Fig. 6 is Cu
46Zr
45Al
7Gd
2The microfracture surface pattern of bulk amorphous alloy compression sample.
Embodiment:
When replacing the Zr element with 2at.%Gd, the overall dimension that this alloy forms amorphous bulk is 8mm, glass transformation temperature (T
g) be 680K, initial crystallization temperature (T
x) be 752K, the temperature of fusion (T of bulk amorphous alloy
m) be 980K, the liquidus temperature (T of bulk amorphous alloy
1) 1178K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 72K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.405.
When replacing the Zr element with 3at.%Gd, the overall dimension that this alloy forms amorphous bulk is 6mm, glass transformation temperature (T
g) be 640K, initial crystallization temperature (T
x) be 748K, the temperature of fusion (T of bulk amorphous alloy
m) be 990K, the liquidus temperature (T of bulk amorphous alloy
1) 1176K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 108K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.412.
When replacing the Zr element with 5at.%Gd, the overall dimension that this alloy forms amorphous bulk is＜6mm glass transformation temperature (T
g) be 646K, initial crystallization temperature (T
x) be 744K, the temperature of fusion (T of bulk amorphous alloy
m) be 1058K, the liquidus temperature (T of bulk amorphous alloy
1) 1160K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 98K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.412.
When replacing the Zr element with 7at.%Gd, the overall dimension that this alloy forms amorphous bulk is＜6mm glass transformation temperature (T
g) be 676K, initial crystallization temperature (T
x) be 746K, the temperature of fusion (T of bulk amorphous alloy
m) be 1056K, the liquidus temperature (T of bulk amorphous alloy
1) 1155K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 70K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.407.
Relevant comparative example 1
Adopt the copper mold teeming practice to prepare Cu
54Ti
18Zr
22Ni
6Bulk amorphous alloy [S.Y. Shin, J.H.Kim, D.M.Lee, J.K.Lee, H.J.Kim, H.G.Jeong, J.C.Bae, New Cu-based bulk metallic glasseswith high strength of 2000MPa, Mater.Sci.Forum, 449-452 (2004) 945].The overall dimension that this alloy forms amorphous bulk is 6mm, glass transformation temperature (T
g) be 712K, initial crystallization temperature (T
x) be 769K, the temperature of fusion (T of bulk amorphous alloy
m) be 1240K, the liquidus temperature (T of bulk amorphous alloy
1) 1287K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 57K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.385.The fracture compressive strength is 2130MPa, total deformation: 3.3%.
Relevant comparative example 2
Adopt the copper mold teeming practice to prepare Cu
50Zr
45Al
5Bulk amorphous alloy [A.Inoue, W.Zhang, Formation, thermal stability and mechanical properties of Cu-Zr-Al bulk glassy alloys, Mater.Tran., 43 (2001) 2921].The overall dimension that this alloy forms amorphous bulk is 3mm, glass transformation temperature (T
g) be 723K, initial crystallization temperature (T
x) be 797K, the liquidus temperature (T of bulk amorphous alloy
1) 1166K, supercooling liquid phase region width (Δ T
x=T
x-T
g) be 74K, form Capability index (γ=T
x/ (T
g+ T
1)) be 0.422.The fracture compressive strength is 2210MPa, yield deformation amount: 0.2%.。
Claims (5)
1. Cu base lump non-crystalline alloy, it is characterized in that: this bulk amorphous alloy is elementary composition by Cu, Zr, four kinds of Al, Gd, and the concrete content of each element is 40～50 atom %Zr, 3～10 atom %Al, 0.2～10 atom %Gd, surplus is Cu.
2. according to the described Cu base lump non-crystalline alloy of claim 1, it is characterized in that each elementary composition scope is: 44.5～45.5 atom %Zr, 6.5～7.5 atom %Al, 1.5～2.5 atom %Gd, the Cu of surplus.
3. the preparation method of the described Cu base lump non-crystalline alloy of claim 1 is characterized in that:
---surperficial non-oxidation, no greasy purity are carried out the weighing mixing greater than four kinds of elements of Cu, Zr, Al, Gd of 99.9%, in the copper crucible in the electric arc furnace of packing into, oxygen absorbent is arranged in the electric arc furnace, in high-purity inert atmosphere, carry out melt back, obtain mother alloy;
---described mother alloy packed into to be had in the silica tube of nozzle, puts into induction furnace and carries out induction melting, in high-purity inert atmosphere, with pressure fused mother alloy molten metal is sprayed in the round-meshed red copper mould, and Circularhole diameter is 2～10mm.
4. according to the preparation method of the described Cu base lump non-crystalline alloy of claim 3, it is characterized in that: described oxygen absorbent is a sponge Ti, and high-purity indifferent gas is an argon gas.
5. according to the preparation method of the described Cu base lump non-crystalline alloy of claim 3, it is characterized in that: the melt back number of times is 4 times, and pressure is 1 ± 0.3MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100462567A CN100368573C (en) | 2005-04-15 | 2005-04-15 | Copper-base lump non-crystalline alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100462567A CN100368573C (en) | 2005-04-15 | 2005-04-15 | Copper-base lump non-crystalline alloy |
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|---|---|
| CN1847424A CN1847424A (en) | 2006-10-18 |
| CN100368573C true CN100368573C (en) | 2008-02-13 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445413C (en) * | 2005-11-01 | 2008-12-24 | 中国科学院物理研究所 | Copper-zirconium based amorphous alloy, and preparation method |
| TWI592946B (en) * | 2016-11-11 | 2017-07-21 | Metal Ind Res & Dev Ct | Copper alloy wire and its manufacturing method |
| CN108118176B (en) * | 2017-12-19 | 2020-07-31 | 中铁建电气化局集团康远新材料有限公司 | Copper-based amorphous alloy for high-speed railway contact line and preparation process thereof |
| CN114480990B (en) * | 2022-01-04 | 2022-07-29 | 河海大学 | Cu-based amorphous powder for cold spraying and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230840A (en) * | 1985-08-02 | 1987-02-09 | Natl Res Inst For Metals | Working substance for magnetic refrigerator and its production |
| US5074935A (en) * | 1989-07-04 | 1991-12-24 | Tsuyoshi Masumoto | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| CN1174823C (en) * | 1999-11-04 | 2004-11-10 | Ykk株式会社 | Method and apparatus for producing cast product with microholes |
-
2005
- 2005-04-15 CN CNB2005100462567A patent/CN100368573C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230840A (en) * | 1985-08-02 | 1987-02-09 | Natl Res Inst For Metals | Working substance for magnetic refrigerator and its production |
| US5074935A (en) * | 1989-07-04 | 1991-12-24 | Tsuyoshi Masumoto | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| CN1174823C (en) * | 1999-11-04 | 2004-11-10 | Ykk株式会社 | Method and apparatus for producing cast product with microholes |
Non-Patent Citations (1)
| Title |
|---|
| Unusual Glass-Forming Ability of Bulk Amorphous AlloysBased on Ordinary Metal Copper. Donghua Xu等.PHYSICAL REVIEW LETTERS,Vol.第92卷 No.第24期. 2004 * |
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| CN1847424A (en) | 2006-10-18 |
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